Ionic Liquid/Deep Eutectic Solvent-Mediated Calcining Synthesis of Cobalt-Based Electrocatalysts for Water Splitting.

The recent advancements of ionic liquids (ILs) and deep eutectic solvents (DESs) in the synthesis of cobalt-based catalysts for water splitting is reviewed. ILs and DESs possess unique physical and chemical properties, serving as solvents, templates, and reagents. Combined with calcination techniques, their advantages can be fully leveraged, enhancing the stability and activity of resulted catalysts. In these solvents, not only are they suitable for simple one-step calcination, but also applicable to more complex multi-step calcination, suitable for more complex reaction conditions. The designability of ILs and DESs allows them to participate in the reaction as reactants, providing metal and heteroatoms, simplifying the preparation system of cobalt phosphide, sulfide, and nitride. This work offers insights into design principles for electrocatalysts and practical guidance for the development of efficient and high-performance materials for hydrogen production and energy storage systems.

Ionic Liquids as Promisingly Multi-Functional Participants for Electrocatalyst of Water Splitting: A Review.

Ionic liquids (ILs), as one of the most concerned functional materials in recent decades, have opened up active perspectives for electrocatalysis. In catalyst preparation, ILs act as characteristic active components besides media and templates. Compared with catalysts obtained using ordinary reagents, IL-derived catalysts have a special structure and catalytic performance due to the influence of IL's special physicochemical properties and structures. This review mainly describes the use of ILs as modifiers and reaction reagents to prepare electrocatalysts for water splitting. The designability of ILs provides opportunities for the ingenious composition of cations or anions. ILs containing heteroatoms (N, O, S, P, etc.) and transition metal anion (FeCl4-, NiCl3-, etc.) can be used to directly prepare metal phosphides, sulfides, carbides and nitrides, and so forth. The special physicochemical properties and supramolecular structures of ILs can provide growth conditions for catalysts that are different from the normal media environment, inducing special structure and high performance. ILs as heteroatom sources are safe, green and easy to operate compared with traditional heteroatom sources. The strategy for using ILs as reagents is expected to realize 100% atomic transformation of reactants, in line with the concept of green chemistry. This review reflects the discovered work with the best findings from the literature. It will offer readers a deeper understanding on the development of IL-derived electrocatalysts and inspire them to ingeniously design high-performance electrocatalysts for water splitting.

Deep Eutectic Solvent-Mediated Electrocatalysts for Water Splitting.

As green, safe, and cheap solvents, deep eutectic solvents (DESs) provide tremendous opportunities to open up attractive perspectives for electrocatalysis. In this review, the achievement of DESs in the preparation of catalysts for electrolytic water splitting is described in detail according to their roles combined with our own work. DESs are generally employed as green media, templates, and electrolytes. A large number of hydrogen bonds in DESs result in supramolecular structures which have the ability to shape the morphologies of nanomaterials and then tune their performance. DESs can also serve as reactive reagents of metal electrocatalysts through directly participating in synthesis. Compared with conventional heteroatom sources, they have the advantages of high safety and designability. The "all-in-one" transformation strategy is expected to realize 100% atomic transformation of reactants. The aim of this review is to offer readers a deeper understanding on preparing DES-mediated electrocatalysts with higher performance for water splitting.

Nonlinear-Optical Crystal Rb3YB6O12 with Condensed B5O10 Blocks That Exhibits an Intriguing Structural Arrangement and a Short Ultraviolet Absorption Edge.

Nonlinear-optical (NLO) crystals, which can regulate the laser wavelength through a cascading second-harmonic-generation technique, have been widely utilized in the field of optoelectronics. In this work, we grew the NLO borate crystal Rb3YB6O12 (RYBO) using the spontaneous crystallization method. RYBO crystallizes in a chiral trigonal space group of R32 with a new type of structural arrangement built from Y-O short chains and B5O10 groups. It is significantly different from the known structure of chemical analogues Rb3REB6O12 (RE = Nd, Eu) not only in the halved unit cell parameter but also in the Y-O connection manner. The NLO response of RYBO is about 0.8KDP, 8-fold larger than that of KB5O8·4H2O with the same B5O10 groups because of the coexistence of two NLO-active units of the distorted YO6 octahedra and B5O10 anions. Thanks to the short ultraviolet (UV) cutoff, RYBO may have potential NLO applications in the UV and even deep-UV spectral regions.

Imidazolium-based ionic liquids grafted on solid surfaces.

Supported ionic liquids (SILs), which refer to ionic liquids (ILs) immobilized on supports, are among the most important derivatives of ILs. The immobilization process of ILs can transfer their desired properties to substrates. Combination of the advantages of ILs with those of support materials will derive novel performances while retaining properties of both moieties. SILs have been widely applied in almost all of fields involving ILs, and have brought about drastic expansion of the ionic liquid area. As green media in organic catalytic reactions, based on utilizing the ability of ILs to stabilize the catalysts, they have many advantages over free ILs, including avoiding the leaching of ILs, reducing their amount, and improving the recoverability and reusability of both themselves and catalysts. This has critical significance from both environmental and economical points of view. As novel functional materials in surface science and material chemistry, SILs are ideal surface modifying agents. They can modify and improve the properties of solids, such as wettability, lubricating property, separation efficiency and electrochemical response. With the achievements in the field of ILs, using magnetic nanoparticles (MNPs) to SILs has drawn increasing attention in catalytic reactions and separation technologies, and achieved substantial progress. The combination of MNPs and ILs renders magnetic SILs, which exhibit the unique properties of ILs as well as facile separation by an external magnetic field. In this article, we focus on imidazolium-based ILs covalently grafted to non-porous and porous inorganic materials. The excellent stability and durability of this kind of SILs offer a great advantage compared with free ILs and IL films physically adsorbed on substrates without covalent bonds. Including examples from our own research, we overview mainly the applications and achievements of covalent-linked SILs in catalytic reactions, surface modification, separation technologies and electrochemistry.

Agaric-like cobalt diselenide supported by carbon nanofiber as an efficient catalyst for hydrogen evolution reaction.

We synthesized herein a novel 3D cathode constructed by growing cobalt diselenide in situ on the surface of carbon nanofiber for hydrogen evolution reaction. The cobalt diselenides with two typical morphologies (agaric-like and nanorod-like) were synthesized by precisely controlling reaction time and temperature in the same system. They show excellent electrocatalytic performance for hydrogen evolution reactions. Especially, the agaric-like diselenide cobalt electrode has the low overpotential (187 and 199 mV) to obtain the current density of 50 and 100 mA cm-2 with a small Tafel slope of 37 mV dec-1 in acidic medium. The excellent catalytic performance of the agaric-like cobalt diselenide can be attributed to its large specific surface area and fast electron transfer rate. More importantly, the agaric-like cobalt diselenide supported carbon nanofiber electrode has excellent long-term stability in electrolyte. The outstanding electrocatalytic performance and stability of agaric-like cobalt diselenide supported carbon nanofiber indicate that it is a promising electrocatalyst for hydrogen evolution reactions.

Reversibly switchable wettability.

This critical review outlines the current state-of-the-art research on the reversibly switchable wettability of surface brought about by external stimuli and the exchange of counterions. Chemical composition and surface topography are the two key factors in the wettability of solid substrates. Applying external stimuli and exchanging counterions of ionic liquids and polyelectrolyte films are valuable approaches for rendering the change in surface chemistry and/or topography, and for driving the transition between hydrophilicity and hydrophobicity of surfaces. Through the combination of stimuli-responsive films and micro-/nanostructural surfaces, smart surfaces with reversible switching between superhydrophobicity and superhydrophilicity have been achieved. As an important advancement in reversibly switchable wettability, this review briefly introduces ionic liquids (ILs) as on-off systems to obtain reversibly switchable wettability and then discusses in more detail the methods to induce the reversibly switchable wettability of surfaces modified by ILs, additives, or thin films. In addition to reversibly switchable wettability mechanisms, open problems and potential solutions are discussed (157 references).

Controllable 1D and 2D Cobalt Oxide and Cobalt Selenide Nanostructures as Highly Efficient Electrocatalysts for the Oxygen Evolution Reaction.

The relationship between controllable morphology and electrocatalytic activity of Co3 O4 and CoSe2 for the oxygen evolution reaction (OER) was explored in alkaline medium. Based on the time-dependent growth process of cobalt precursors, 1D Co3 O4 nanorods and 2D Co3 O4 nanosheets were successfully synthesized through a facile hydrothermal process at 180 °C under different reaction times, followed by calcination at 300 °C for 2 h. Subsequently, 1D and 2D CoSe2 nanostructures were derived by selenization of Co3 O4 , which achieved the controllable synthesis of CoSe2 without templating agents. By comparing the electrocatalytic behavior of these cobalt-based catalysts in 1 m KOH electrolyte toward the OER, both 2D Co3 O4 and 2D CoSe2 nanocrystals have lower overpotentials and better electrocatalytic stability than that of 1D nanostructures. The 2D CoSe2 nanosheets require overpotentials of 372 mV to reach a current density of 50 mA cm-2 with a small Tafel slope of 74 mV dec-1 . A systematic contrast of the electrocatalytic performances for the OER increase in the order: 1D Co3 O4 <2D Co3 O4 <1D CoSe2 <2D CoSe2 . This work provides fundamental insights into the morphology-performance relationships of both Co3 O4 and CoSe2 , which were synthesized through the same approach, providing a solid guide for designing OER catalysts.

Synthesis of biaryls and polyaryls by ligand-free Suzuki reaction in aqueous phase.

A highly efficient palladium acetate-catalyzed ligand-free Suzuki reaction in aqueous phase was developed in short reaction times (0.5-1 h) at 35 degrees C in air. The key for such a successful catalytic system was the use of a suitable amount of cosolvents in the aqueous phase. The method could be extended to the consecutive multi-Suzuki coupling, and polyaryls were prepared in a single one-pot step in high selectivity and excellent yield under mild reaction conditions (60 degrees C).

Phosphine-free cross-coupling reaction of arylboronic acids with carboxylic anhydrides or acyl chlorides in aqueous media.

The palladium acetate-catalyzed coupling reaction of aryl boronic acid with carboxylic anhydride or acyl chloride was carried out smoothly in water in the presence of poly(ethylene glycol) (PEG) or 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) to give high yields of ketones without the use of phosphine ligands. The Pd(OAc)2-H2O-[bmim][PF6] catalytic system can be recovered and reused eight times with high efficiency for both carboxylic anhydride and acyl chloride.